EP0551837A1 - Polyäthylen-Verbundstoffe - Google Patents

Polyäthylen-Verbundstoffe Download PDF

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Publication number
EP0551837A1
EP0551837A1 EP93100225A EP93100225A EP0551837A1 EP 0551837 A1 EP0551837 A1 EP 0551837A1 EP 93100225 A EP93100225 A EP 93100225A EP 93100225 A EP93100225 A EP 93100225A EP 0551837 A1 EP0551837 A1 EP 0551837A1
Authority
EP
European Patent Office
Prior art keywords
composite
temperature
polyethylene
molecular weight
ultrahigh molecular
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP93100225A
Other languages
English (en)
French (fr)
Inventor
Daniel Wagner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yeda Research and Development Co Ltd
Original Assignee
Yeda Research and Development Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yeda Research and Development Co Ltd filed Critical Yeda Research and Development Co Ltd
Publication of EP0551837A1 publication Critical patent/EP0551837A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D06M10/025—Corona discharge or low temperature plasma
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/50—Modified hand or grip properties; Softening compositions

Definitions

  • the invention is in the field of synthetic polyhydrocarbon composite material and concerns specifically composite polyethylene materials with fiber reinforcement.
  • Such reinforced composites are prepared by immersing a fibrous structure such as a two-or three-dimensional grid, a fabric or a non-woven fiber mat into a body of molten polymeric thermoplastic material and inducing the latter to crystallise, by cooling, whereby the plastic material crystallises to form a polymer matrix with a reinforcing fibrous structure embedded therein.
  • spherulites (1) which are sphere-shaped crystalline structures that grow progressively from random points in the melt until they finally impinge upon each other and fill the entire mass of material. This form of nucleation and growth is occasionally termed as homogeneous and is the one usually observed in the solidification of molten polymer material in bulk.
  • a heterogeneous mode of crystallisation may occur.
  • the process starts from nucleation sites on the surface of the foreign object, e.g. a fiber where the growth occurs in a direction transversal to the axis of the fiber, resulting in the formation of a laminar layer often referred to as a transcrystalline layer.
  • transcrystalline layers function as interfaces between the polymer matrix and the reinforcing fibrous structure.
  • the existence of such transcrystalline interfaces has been observed in composites of a number of polymers such as isotactic polypropylene with E-glass fibers (2); poly(ether ether ketone) (3), the so-called J-polymer (4), polyphenylene sulfide (5), all with carbon fibers, polyethylene with polyethylene fibers (6); and polyethylene with carbon fibers (7).
  • Polyethylene is a cheap and lightweight polymer which is manufactured and used on a very large scale for a host of different purposes.
  • the mechanical properties of polyethylene are, however, unsatisfactory and it suffers inter alia from relatively low impact resistance and poor mechanical strength.
  • ultrahigh molecular weight polyethylene has a very high impact resistance and a specific mechanical strength which surpasses even that of KevlarTM, but so far attempts to use ultrahigh molecular weight polyethylene fibers as a reinforcement for making composites failed because of its inability of efficient interface bonding.
  • the present invention is based on the observation that upon a short preliminary treatment with oxygen plasma, ultrahigh molecular weight polyethylene fibers immersed in molten low density polyethylene are capable, upon cooling of the melt, to induce the formation of a transcrystalline layer of polyethylene.
  • the invention provides a composite comprising a low density polyethylene matrix and a reinforcing structure of ultrahigh molecular weight polyethylene fiber held together by a transcrystalline interface layer between fiber and matrix.
  • the reinforcing structure of ultrahigh molecular weight polyethylene fibers may be of any suitable shape such as, for example, two-or three-dimensional grids, a fabric, a non-woven fiber mat and the like.
  • the molecular weight of the ultrahigh molecular weight polyethylene used as reinforcing fibers in accordance with the present invention is above 106.
  • ultrahigh molecular weight polyethylene for making reinforcing fibrous structures for the purposes of the present invention are Spectra 1000TM, DyneemaTM and TekmilonTM.
  • the thickness of a transcrystalline layer in a composite according to the invention will be within the range of about 1 ⁇ m to about 40 ⁇ m.
  • the temperature at which the matrix is solidified may be room temperature or above.
  • the exposure of the reinforcing structure of ultrahigh molecular weight polyethylene fibers to oxygen plasma lasts, as a rule, several minutes only and the duration of such exposure should, in any event, be so limited that the mechanical properties of the ultrahigh molecular weight polyethylene fibers are not adversely affected in any significant way.
  • oxygen plasma produced with a 60 W radiofrequency generator and delivered at a rate of 10 cc/min., a five minute exposure is sufficient to produce the desired activation.
  • Step (ii) - the melt is maintained at a temperature within the range of 128°C-143°C, e.g. at 135°C.
  • Step (iv) - the composite precursor is cooled to a transcrystallisation temperature within the range of 109°C to 116°C, e.g. to 115°C and maintained at that temperature until a desired degree of transcrystallinity is obtained;
  • Step (v) the composite precursor with trans-crystalline layers on the fibers resulting from step (iv), is cooled down to room temperature and allowed to solidify.
  • cooling down from the first melting temperature of the polyethylene melt to the transcrystallisation temperature at which the transcrystalline layers form should be rapid, say at the order of 30°C/min.
  • step (ii) should be held as short as possible, say several minutes, so as to avoid oxidation of the polyethylene matrix.
  • this cycle may be repeated several times.
  • EXAMPLE 1 Preparation of a single fiber composite polymer of ultrahigh molecular weight polyethylene and linear low density polyethylene
  • a bundle of Spectra 1000TM (Allied) ultrahigh molecular weight polyethylene fibers having a diameter of 38 ⁇ m was pretreated with oxygen plasma using a glow discharge plasma cleaner (Harrick). To this end, the fiber bundle was first cleaned in acetone and then wound on a glass frame and introduced into the chamber of the plasma cleaner. The chamber was then evacuated to 100 mtorr followed by flashing with oxygen with continuous evacuation until the vacuum was about 40 mtorr. The flow controller was then set to the desired flow rate of 10cc/min. and the 60 W radiofrequency generator turned on. A white glow, typical of oxygen, appeared after 30 sec. and the fibers were exposed for 5 min. more.
  • the oxygen flow and the plasma generator were switched off and atmospheric pressure was restored within the chamber.
  • the glass frame with the fibers was withdrawn and the fibers were removed from the frame.
  • FIG. 1 Video pictures of three phases in the growth of the transcrystalline layer in one single fiber composite prepared as above, is shown in Fig. 1.
  • EXAMPLE 2 The growth kinetics of the transcrystalline layer in a composite material prepared according to the present invention

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
EP93100225A 1992-01-10 1993-01-08 Polyäthylen-Verbundstoffe Withdrawn EP0551837A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IL100630A IL100630A0 (en) 1992-01-10 1992-01-10 Polyethylene composites
IL100630 1992-01-10

Publications (1)

Publication Number Publication Date
EP0551837A1 true EP0551837A1 (de) 1993-07-21

Family

ID=11063257

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93100225A Withdrawn EP0551837A1 (de) 1992-01-10 1993-01-08 Polyäthylen-Verbundstoffe

Country Status (2)

Country Link
EP (1) EP0551837A1 (de)
IL (1) IL100630A0 (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0714460A1 (de) * 1993-08-20 1996-06-05 Smith & Nephew, Inc. Selbstverstärkte verbundwerkstoffe aus polyethylen mit sehr hohem molekulargewicht
US5972484A (en) * 1997-12-01 1999-10-26 Polyeitan Composites Ltd. Ultrahigh molecular weight polyethylene composite for printed circuit board and antenna base material
US6132657A (en) * 1998-06-29 2000-10-17 Polyeitan Composites Ltd. Process for producing polymeric materials
US6168855B1 (en) 1997-12-01 2001-01-02 Polyeitan Composites Ltd. Polyolefin composites for printed circuit board and antenna base material
US20140272436A1 (en) * 2013-03-14 2014-09-18 Honda Motor Co., Ltd. Bonded body made from different materials and method for producing the same
WO2017060469A1 (en) * 2015-10-09 2017-04-13 Dsm Ip Assets B.V. High performance fibres composite sheet
CN112959761A (zh) * 2021-02-10 2021-06-15 浙江沪通模具有限公司 一种高强度的低介电常数低介质损耗复合材料及制备方法
WO2024100611A1 (en) * 2022-11-10 2024-05-16 Ariel Scientific Innovations Ltd. Microcomposite comprising a nucleating component and a thermoplastic polymer

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0089502A2 (de) * 1982-03-19 1983-09-28 AlliedSignal Inc. Komposite enthaltend Polyolefinfasern und Polyolefinmasse
EP0282220A2 (de) * 1987-03-02 1988-09-14 Mitsui Petrochemical Industries, Ltd. Polyolefin-Formgegenstand und Verfahren zu seiner Herstellung

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0089502A2 (de) * 1982-03-19 1983-09-28 AlliedSignal Inc. Komposite enthaltend Polyolefinfasern und Polyolefinmasse
EP0282220A2 (de) * 1987-03-02 1988-09-14 Mitsui Petrochemical Industries, Ltd. Polyolefin-Formgegenstand und Verfahren zu seiner Herstellung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF APPLIED POLYMER SCIENCE vol. 22, 1978, pages 3249 - 3265 MEAD W.T. & PORTER R.S 'POLYETHYLENE COMPOSITES' *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0714460A1 (de) * 1993-08-20 1996-06-05 Smith & Nephew, Inc. Selbstverstärkte verbundwerkstoffe aus polyethylen mit sehr hohem molekulargewicht
EP0714460A4 (de) * 1993-08-20 1998-01-07 Smith & Nephew Richards Inc Selbstverstärkte verbundwerkstoffe aus polyethylen mit sehr hohem molekulargewicht
US5972484A (en) * 1997-12-01 1999-10-26 Polyeitan Composites Ltd. Ultrahigh molecular weight polyethylene composite for printed circuit board and antenna base material
US6168855B1 (en) 1997-12-01 2001-01-02 Polyeitan Composites Ltd. Polyolefin composites for printed circuit board and antenna base material
US6132657A (en) * 1998-06-29 2000-10-17 Polyeitan Composites Ltd. Process for producing polymeric materials
US9403344B2 (en) * 2013-03-14 2016-08-02 Honda Motor Co., Ltd. Bonded body made from different materials and method for producing the same
US20140272436A1 (en) * 2013-03-14 2014-09-18 Honda Motor Co., Ltd. Bonded body made from different materials and method for producing the same
WO2017060469A1 (en) * 2015-10-09 2017-04-13 Dsm Ip Assets B.V. High performance fibres composite sheet
CN108137827A (zh) * 2015-10-09 2018-06-08 帝斯曼知识产权资产管理有限公司 高性能纤维复合片材
JP2018535847A (ja) * 2015-10-09 2018-12-06 ディーエスエム アイピー アセッツ ビー．ブイ．Ｄｓｍ Ｉｐ Ａｓｓｅｔｓ Ｂ．Ｖ． 高性能繊維複合シート
US11149122B2 (en) 2015-10-09 2021-10-19 Dsm Ip Assets B.V. High performance fibres composite sheet
CN112959761A (zh) * 2021-02-10 2021-06-15 浙江沪通模具有限公司 一种高强度的低介电常数低介质损耗复合材料及制备方法
WO2024100611A1 (en) * 2022-11-10 2024-05-16 Ariel Scientific Innovations Ltd. Microcomposite comprising a nucleating component and a thermoplastic polymer

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Publication number Publication date
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